Starch based polyether polyols

ABSTRACT

A STARCH BASED POLYOL FOR POLYURETHANES IS DESCRIBED WHICH IS MADE BY REACTING CORNSTARCH WITH GLYCOL ETHERS AND ALKOXYLATING THE RESULTING REACTION PRODUCT.

United States Patent 3,721,665 STARCH BASED POLYETHER PoLYoLs vPhilip Hotchkiss Moss and Michael Cuscurida, Austin,

Tex., assignors to Jefferson Chemical Company, Inc., Houston, Tex.

No Drawing. Original application June 29, 1970, Ser. No. 50,901. Divided and this application Oct. 7, 1971, Ser.

Int. or. cost 19/06 U.S. Cl. 260233.3 R 8 Claims ABSTRACT OF THE DISCLOSURE A starch based polyol for polyurethanes is described which is made by reacting cornstarch with glycol ethers and alkoxylating the resulting reaction product.

CROSS REFERENCE TO RELATED APPLICATION This is a division of application Ser. No. 50,901 filed June 29, 1970, now Pat. No. 3,655,590.

It is known in the art to use alkylene oxide adducts of glycosides as intermediates for rigid polyurethane foam. However, high cost, high viscosity or processing difficulties have limited the usefulness of these products.

Polyols have been prepared from cornstarch reacted with ethylene glycol to form a glycoside which is then alkoxylated to a polyether. However, these products are difiicult to make requiring high temperatures and excessive time for stripping the excess ethylene glycol in the glycoside preparation stage. Also, these polyethers are very viscous, 30,00037,500 centipoises (cps.)' and, therefore, difiicult to use in rigid foam manufacturing. The process of the invention overcomes these problems and allows low viscosity, 7,50015,000 cps., starch-based polyols to be made easily.

Polyethers based on methyl glycoside reacted with an alkylene oxide are known in the art, but in the hydroxyl number range necessary for rigid foam manufacture, the methyl glycoside polyethers are very viscous. Also, methyl glycoside is not an economical starting material for urethane polyols.

SUMMARY OF THE INVENTION The invention is a new starch-based polyol for poly- DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyhydroxy polyether polyol of the invention may be prepared by reacting over an acid catalyst with sufice ficient heat to effect the reaction, one mole of starch (basis anhydroglucose units), preferably cornstarch, with from about two to about four moles of a glycol ether of the type R(OCH CH ),,OH wherein R is an alkyl group of l to 4 carbon atoms and n is equal to one or two. The glycoside product of this reaction is then neutralized and stripped of water and excess glycol ether. The glycoside is then alkoxylated to the final polyol over a basic catalyst at a temperature sufficient to sustain the reaction. The alkylene oxide may be ethylene oxide, propylene oxide, or butylene oxide. Propylene oxide is preferred. The hydroxyl number which is desired for the finished polyol will determine the amount of alkylene oxide to react with the glycoside. The hydroxyl number may range from about 300 to about 500 but the preferred range is from about 350 to about 450. The reaction mixture is then neutralized and the water and excess reactants are stripped from the polyol.

In order to form polyurethane foams using the polyols prepared as above described, several other ingredients are essential: first an isocyanate. An isocyanate reacts directly with the active hydrogens of the polyol. The isocyanate may be difunctional such as toluene diisocyanate or the polyfunctional polyaryl isocyanates. These polyaryl isocyanates are produced by the phosgenation of the reaction product of aniline and formaldehyde. Such reactions are well known and described in Us. Pats. 2,683,730, 3,277,173, 3,344,162 and 3,362,979, for example. The polyaryl isocyanates thus formed have functionalities greater than two which can be varied up to the higher functionality materials. In practice, however, functionalities greater than four are attained only with difficulty. However, for purposes of practice of my invention, materials with a functionality as high as five may be used. It is preferred that the functionality be from two to about four, and especially preferred that the functionality of the polymethylene polyphenyl isocyanate used in the practice of my invention be from about 2.3 to about 3.5.

In the production of polyurethane foams in the practice of my invention, other known additives are ncessary. One such constituent is the blowing agent. Some examples of such material are trichloromonoiluoromethane, dichlorodifiuoromethane, dichloromonofluoromethane, 1,1- dichloro-l-fluoromethane, 1,1-difiuoro 1,2,2 trichloromethane, chloropentafluoroethane, and the like. Other useful blowing agents include low-boiling hydrocarbons such as butane, pentane, hexane, cyclohexane, and the like. See US. Pat. 3,072,582, for example.

Many catalysts of urethane formation are useful in the practice of my invention. Such catalysts which either may be used alone or in combination with other catalysts are, for example, dimethylaminoethanol, tetramethyl-l, 3-propanediamine, triethylenediamine, tetramethyl-1,3- butanediamine, dimethylethanolamine, methyltriethylenediamine, N-methylmorpholine, N-ethylmorpholine, and the like. There are many tertiary amine catalysts which are useful and well known to those skilled in the art both as to the proportion which should be used and the catalyst compounds themselves. The catalyst is employed in catalytic amounts such as from about 0.1 wt. percent to about 6 wt. percent based upon the weight of the polyol.

Surfactant agents, better known as silicone oils, are added to serve as a cell stabilizer. Some representative materials are sold under the names of SF-1109, L-520, L-521 and DC-193 which are, generally, polysiloxane polyoxyalkylene blocked copolymers, such as those disclosed in US. Pats. 2,834,748, 2,917,480 and 2,846,458, for example.

Should fire retardancy be required for the polyurethane foam, two types of fire retardants are available: those that are incorporated by mere mechanical mixing and those that become chemically bound in the polymer chain. Representative of the first type are tris(chloroethyl) phosphate, tris(2,3-dibromopropyl) phosphate, diammonium phosphate, various halogenated compounds and antimony oxide. Representative of the chemically bound type are chlorendic acid derivatives, and various phosphorous-containing polyols.

There are two well known methods suitable for the manufacture of the polyurethane foam of this invention the one shot method and the prepolymer method.

In the one shot method, all of the components are mixed together at once and the reaction is in one step. In the prepolymer method, only a portion of the polyol is initially reacted with the isocyanate to form a so-called prepolymer. When foam is desired the rest of the polyol and the other ingredients are added to this prepolymer and the foam is formed. Both methods have advantages and drawbacks and it is within the understanding of one skilled in the art to select the method most desirable under specific circumstances.

The following examples are designed to illustrate the invention and its advantages without limiting its scope.

Example I illustrates the preparation of three polyols of the invention. Examples II, III, and IV illustrate prior art polyols and the problems involved in their preparation. Example V illustrates the preparation of rigid foams from the polyols like those in Examples I1V to show that excellent foams may be prepared from the polyols of the invention.

EXAMPLE I This example will illustrate the preparation of a 398 hydroxyl number propylene oxide adduct of a glycoside prepared by the sulfuric acid-catalyzed reaction of cornstarch with ethylene glycol monomethyl ether. Into a ten gallon kettle was charged lb. cornstarch, 22.5 lb. ethylene glycol monomethyl ether and 28 g. concentrated sulfuric acid. The reactor was then thoroughly purged with prepurified nitrogen. The reaction mixture was then heated to 125 C. and kept at that temperature for two hours. After cooling to 75 C. the product was neutralized with 17 g. flaked potassium hydroxide. Excess ethylene glycol monomethyl ether and water (20.9 lb. total) were removed by vacuum stripping to a minimum pressure at 100 C. Approximately two hours were required to strip the excess glycol ether. Potassium hydroxide (151 g.) catalyst was then added and the methoxyethyl glycoside 16.6 lb.) was propoxylated with propylene oxide (28 lb.) at 125-130 C. at 60 p.s.i.g. Approximately two to three hours were required for addition of the propylene oxide. The reaction mixture was then digested to an equilibrium pressure and stripped with nitrogen for one-half hour. The alkaline product was then diluted to 60-70% nonvolatiles with water. After filtering through a filter cloth, the aqueous product was passed in sequence through acidic (Amberlite 200) and basic (Duolite 102-D) ionexchange columns. The product was dewatered by stripping to 110 C. at a minimum pressure and then with nitrogen for one-half hour. The dewatered product was then polish filtered. It had the following properties:

POLYOL la Acid number, mg. KOH/g. 2.0 Hydroxyl number, mg. KOH/g. 398 Water, wt. percent 0.09

Using the above procedure, polyethers have hydroxyl numbers of 405 and 423 were prepared by propoxylation of the glycoside from the starch-ethylene glycol monomethyl ether reaction. Charges and polyether properties are shown in the following table:

Polyol lb 10 Charge:

Corn starch, lb 16 16 Ethylene glycol monomethyl ether, lb 22. 6 22. 5

Sulfuric acid, conc., g 28 28 Potassium hydroxide, flaked For neutralizatiom. 17 17 For catalysis 151 141 Propylene oxide, lb 28 24 Properties:

Acid number, mg. KOH/g 1. 2 1. 4

Hydroxyl number, mg. KOH/g- 405 423 Water, wt. percent 0. 04 .04

Viscosity, 25 0., cps 9,400 15,000

Ash, wt. percent. 0.015 0. 7

Sodium, p.p.m-.-- 137 3. 6

Potassium, p.p.m 4. 7 4.0

EXAMPLE II This example illustrates the preparation of polyethers by propoxylation of ethylene glycol glycosides. It will further show processing difficulties associated with the preparation of these products and the high viscosities of the finished product.

Into a ten-gallon kettle were charged 22.5 lb. ethylene glycol, 15 lb. cornstarch, and 30 g. concentrated sulfuric acid. The reactor was then evacuated and purged with prepurified nitrogen. The reaction mixture was digested one to three hours at -130 C. and neutralized at 95 C. with 16.4 g. potassium hydroxide. Water and ethylene glycol were then removed by stripping at 160 C. at minimum pressure. Stripping times ranged from three to six hours in a ten-gallon reactor to 36 hours in a l000-gal1on reactor. Potassium hydroxide (157 g.) catalyst was added and the glycoside was propoxylated (35.16 lb.) at 160" C. at 60 p.s.i.g. Approximately two hours were required for addition of the propylene oxide. The reaction mixture was then digested to an equilibrium pressure and stripped with nitrogen for one-half hour. The alkaline product was diluted to 60-70% nonvolatiles with water. Hyfio Supercel (100 g.) and di-t-butyl p-cresol (19 g.) were also added at this time. After filtering, the aqueous product was passed in sequence through acidic (Amberlite 200) and basic (Duolite 102-D) ion-exchange columns. The product was dewatered by stripping to 100 C. at minimum pressure and then with nitrogen for one-half hour. The dewatered product was then polish filtered. The properties were as follows:

POLYOL 2a Acid number, mg. KOH/g. 0.06 Hydroxyl number, mg. KOH/g. 4'05 Viscosity, 25 C., cps. 32,500 Water, wt. percent 0.02 Sodium, p.p.m. 1.1 Potassium, p.p.m. 8.3 A'sh, wt. percent Nil pH in 10:6 isopropanol-water 6.2

Using the above procedure, a 427 hydroxyl number propylene oxide adduct of a starch glycoside was pre- Although propylene oxide adducts of the ethylene glycol glycosides are interesting rigid foam intermediates, there are several difiiculties associated with their manufacture and use. Included are the long ethylene glycol stripping times (up to 36 hours in larger equipment) and high temperatures required for stripping (165 C.). The long stripping time's offset any advantages in raw material costs. In addition, the high viscosity of the products (32,000- 36,000 cps. at 25 C.) in the useful hydroxyl number range (405-421) presents problems in foam manufacture.

EXAMPLE III Polyethers based on methyl glycoside have been extensively studied as rigid foam intermediates. Although generally satisfactory, several disadvantages are associated with their use. Included are the high cost of methyl glycoside, processing problems, and high viscosity products.

The preparation of a typical methyl glycoside polyol can be described as follows:

Into a ten-gallon kettle were chaged 31.25 lb. of a 75% aqueous methyl glycoside solution and 227 g. flaked potassium hydroxide. The kettle was then evacuated, purged with prepurified nitrogen, and heated to 125 C. Propylene oxide (7.46 lb.) was then added at' 125-135" C. over a -minute period. The reaction mixture was then digested to an equilibrium pressure and additional propylene oxide (37.32 lbs.) was added and digested. The product could be neutralized with 85% phosphoric acid or the potassium removed by passage through an acidic ion-exchange column. The product was then dewatered and filtered. Properties of the finished product were as follows:

6 Acid number, mg. KOH/g. 0.2 Hydroxyl number, mg. KOH/g 417 Viscosity, 25 C., cps 31,500 Water, wt. percent 0.04 Ash, wt percent Nil Sodium, p.p.m. 0.4 Potassium, p.p.m. 1.5 pH in 10:6 isopropanol-water 4.3

EXAMPLE IV Using the procedure of Example IH, a 410 hydroxyl number propylene oxide adduct of an experimental mixture of alphaand beta-methyl glucosides has been prepared. Charges and product properties as as follows:

Charge:

70.8% aqueous solution of alphaand betamethyl glucosides, lb. 35.3

Potassium hydroxide, flaked, g 227 Propylene oxide, step 1, lb. 7.48 Propylene oxide, step 2, 1b 37.32

Properties:

Acid number, mg. KOH/ g. 0.7 Hydroxyl number, mg. KOH/ g. 410 Viscosity, 25 C., cps. 37,500 Water, wt. percent 0.03 Ash, wt. percent 0.002 Sodium, p.p.m. 0.2 Potassium, p.p.m. 0.8 pH in 10:6 isopropanol-water 5.7

The high viscosity of this polyol presents an obvious disadvantage to its use in foam preparation.

EXAMPLE V This example will illustrate the preparation of rigid foams from the polyols described in Examples I-V. It further shows that foams with good properties can be prepared from polyols derived from the methoxyethyl glycosides'of'Example I. In addition, this example shows that foams from the polyols of our invention are as good as those derived from Examples II-IV. This is accompanied by the forementioned advantages in cost, processing, and product viscosity. The tests performed and shown in the tables below on the foams are reported in the American Society for Testing and Materials (ASTM) and the ASTM designations are shown in the tables.

Foam No 6a 5b 5c lid Formulation, p.b.w.:

Polyol of Example Ib (OH-=405) 41.8 33. 2 Polyol of Example 1c (OH=423) 41 32. 7 Silicone oil 0. 5 0. 5 0. 6 0. 5 Diethyl b1s(2 -hydroxyethy1) aminomethanephosphonate 8. 0 8. 0 Dlmethylaminoethanol 0. 5 o. 5 o. 5 0. 5 Tetrarnethyl 1,3-propanediamine- 0.5 0.5 0. 6 0. 5 Fluorocarbon 11b 14 14 14 14 Polyaryl lsooyanate 42. 7 43. 3 43. 5 44 Detailspf preparation: 7

Cream time, see. (time to beginning of reaction) 38 20 30 28 Rise time, sec 190 210 210 Tack-free time, see. (time when foam is not sticky to the touch) 150 100 160 Properties:

Density, p.c.i. (ASTM D1622-63) 1. 9 1. 8 1. 8 1. 8 Compressive strength, p.s.i. (ASTM D1621):

Parallel- 34. 5 30 33 33 Perpendicular 11 9 9. 7 10. 2 Tensile strength, p.s.i. (ASTM D1623). 50 3. 6 4t. 4 45. 9 Burning rate, in lmin. (ASTM D1692-2 1 5. 5 1 4(33. 4) 5.3 1. 5(34. 2) K-tactor (ASTM 0177-63) 0.136 0.132 0. 132 0.128 Dimensional stability (ASTM D2126):

168 F., 100% R.H.:

Avolume:

24 hoi l rs 1g. 4 16.23 17. 0 $3. 0 wee .6 3. l. 4 Aweight: 3

24 hours -10. 0 2. 9 1. l. 1.1 1 week 2.4 2. 9 2. 3 2. 6 Alinear:

24 ho r 6. 8 9. o 7. 4 1 week 10. 4 14. 6 8. 7 12. 9 F., dry, 1 week:

A ll. 5 6. 6 6. 0 4. 6 A 0. 5 0. l 0. l 0. 2 AL" 3.6 4.1 4.0 3.6

per mole of anhydroglucose unit of said starch of a glycol ether of the formula R(OCH CH OI-I wherein R is an alkyl group of 1 to 4 carbon atoms and n is equal to one or two. an then alkoxylating, over a basic catalyst at a temperature sufficient to sustain the reaction, the glycoside product of this reaction to give a polyol having a hydroxyl number of at least 350. 2. The polyhydroxy polyether polyol of claim 1 wherein the glycol ether is ROCH CH OH and R is an alkyl group of l to 4 carbon atoms.

3. The polyhydroxy polyether polyol of claim 2 wherein wherein R is an alkyl group of 1 to 4 carbon atoms and n is equal to one or two and then TABLE-Continued Foam N 5e 5! 5g 5h 7 51 51' gill i i i 1 1a 1 m l E 1 II yene gyco gycos e poye er as n xampe (OH=427) 251 220 Methyl glueoside polyol as in Example IV (0H=407) 251. 7 188. 7 Methyl glucoside polyol as in Example III (0H=427) 251. 7 157. 2 Formulation, p.b.w.:

Diethyl bis(Z-hydroxyethyl)aminomethylphosphonate 90 Silicone nil 3.0 3.0 3.0 .0 3.0 Dimethylaminoethanol 3.6 3.0 3. 6 1. 8 1. 6 Tetramethyi1,3-pr p n 3 3.6 1.8 1.6 Trlchloromonofluoromethane 85 81 81 Polyaryl isoey tn 258 260 257. 1 260. 1 257. 1 261.6 Details of preparation:

Cream time, w 24 28 as 22 12 Rise time, see 130 190 120 180 145 104 Tack-free time, see 140 205 100 180 112 Properties:

Density, p.01. (AS'IM D1022-63) 2. 2 2. 2 2. 0 1. 9 2. 1 I 1. 9 Compressive strength, p.s.i. (ASTM D1621):

Parallel 34 40 33 42 32 Perpendicular 15 15 16 16 17 12 Tensile strength, p.s.l. (ASTM D1625) 49 62 47 58 56 51 Burning rate, in./min. (ASTM DEW-68).. l 7. 3 1 1. 1 l 6. 5 i 1. 1 1 4.0 K-factor (ASTM C177-63 0. 113 '0. 111 0. 0. 117 Dimensional stability (ASTM D2126):

168 F., 100% R.H.:

Avolume:

24 hours 5. 4 l5. 1 7. 1 l6. 7 7. 4 20. 1 1 week 8- 0 9.2 12. 4 24. 2 13. 4 33. 9 Aweight:

24 hnnre 0. 4 -0- 5 '1- 5 1. 6 -1. 7 -3.0 1 week --1. 8 --1. 6 5. 0 -2. 4 1. 9 --4. 7 Alinear:

24 hours 3. 9 3. 4 4. 3 8. 8 5. 1 11. 7 5.9 5.9 6.8 12.3 7.7 V 18.4 F., dry, 1 week:

AV 3.3 3.5 5.5 4.7 5.6 7.4 w 0. 2 0. 1 -0. 7 0. 4 1.4 2. 2 AL 2. 0 2.4 5. 5 r. 9 a. 8 4. 7

1 Burns. I S.E. F.R.

I claim: alkoxylatmg, over a basic catalyst at a temperature suf- 1. A polyhydroxy polyether polyol of starch prepared ficient to sustain the reaction, the glycoside product by reacting starch over an acid catalyst with sufiiclent heat of this reaction to give a polyol having a hydroxyl to effect the reaction with from about 2 to about 4 moles 35 number of at least 350,

6. The method of claim 5 wherein the glycol ether is ROCH CH OH and R is an alkyl group of 1 to 4 carbon atoms.

7. The method of claim 6 wherein the glycol ether is CH OCH CH OH.

8. The method of claim 7 wherein the alkylene oxide is propylene oxide and the starch is cornstarch.

References Cited UNITED STATES PATENTS 3,165,508 1/1965 Otey et a1 260-210 3,402,170 9/1968 Fuzesi et al 260-2333 3,505,255 4/1970 Granger et al. 260-9 3,510,471 5/1970 Case 260-209 3,541,034 11/1970 Fuzesi et al 260-25 3,655,590 4/1972 Moss et al. 260-25 AS DONALD E. CZAJA, Primary Examiner M. I. MARQUIS, Assistant Examiner US. Cl. X.R.

260-25 AS, 233.3 R, 233.3 A, 233.5 

